Thin glass/metal laminate with anti-glare surface

ABSTRACT

Disclosed herein are laminated structures comprising a metal sheet including a first face and a second face with a thickness of from about 0.5 mm to about 2 mm extending between the first face and the second face. The laminated structure further includes a first chemically strengthened or non-chemically strengthened glass sheet including a thickness of less than or equal to about 2 mm and a first interlayer attaching the first glass sheet to the first face of the metal sheet. Also disclosed herein are methods of manufacturing a laminated structure comprising the steps of laminating a metal sheet and a first glass sheet together with an interlayer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of International PatentApplication No. PCT/US2013/062956, filed on Oct. 2, 2013, which claimsthe benefit of priority to U.S. Provisional Application No. 61/710,287filed on Oct. 5, 2012, the contents of which are incorporated herein byreference in their entireties.

FIELD OF THE DISCLOSURE

Disclosed herein are glass/metal laminated structures and methods ofmanufacturing laminated structures and, more particularly, glass/metallaminated structures including a chemically strengthened ornon-chemically strengthened glass sheet and methods of manufacturinglaminated structures including a chemically strengthened ornon-chemically strengthened glass sheet.

BACKGROUND

A variety of apparatuses, such as appliances, may comprise an outerhousing including a metal sheet. For example, relatively thin metalsheets can be used as an outer housing surface for an appliance such asa refrigerator and/or freezer. As such, the metal sheet may protect theappliance while also maintaining the outer appearance of the appliance.However, it has been observed that the metal outer housing sheet maylose its aesthetic appearance over time due to poor scratch resistanceand/or cleaning difficulties, for example, with respect to fingerprintsand/or oil smudges. Accordingly, it would be advantageous to provide ametal sheet with a protective skin, such as a thin glass/metal laminatedstructure, which can be more easily cleaned and/or which may haveincreased scratch resistance. It would also be advantageous to providesuch laminated structures with improved aesthetic properties, such as ananti-glare and/or antimicrobial surface.

SUMMARY

The disclosure relates, in various embodiments, to a laminated structurecomprising a metal sheet including a first face and a second face with athickness ranging from about 0.1 mm to about 5 mm extending between thefirst face and the second face. The laminated structure further includesa first chemically strengthened or non-chemically strengthened glasssheet including a thickness ranging from about 0.3 mm to about 2 mm anda first interlayer attaching the first glass sheet to the first face ofthe metal sheet.

In certain embodiments, the first interlayer may comprise polyvinylbutyral or an ionomer. The first interlayer may, in various embodiments,have a thickness ranging from about 0.1 mm to about 2 mm, such as fromabout 0.1 mm to about 0.8 mm. In further embodiments, the firstinterlayer may have a Young's modulus of greater than or equal to 15MPa, such as greater than or equal to 275 MPa.

According to other non-limiting embodiments, the first glass sheet mayhave a thickness ranging from about 0.5 mm to about 1.1 mm. The firstglass sheet may, in various embodiments, be chemically strengthened andmay comprise a glass selected from the group consisting ofaluminosilicate glass and alkali-aluminoborosilicate glass. The firstglass sheet may also comprise, by way of non-limiting example, ananti-glare surface which may be obtained, for instance, by etching-basedand/or sol gel processes.

The disclosure also relates to a method of manufacturing a laminatedstructure comprising: (i) providing a metal sheet including a first faceand a second face having a thickness ranging from about 0.1 mm to about5 mm extending between the first face and the second face, (ii)providing a chemically strengthened or non-chemically strengthened glasssheet having a thickness of less than or equal to about 2 mm and atleast one anti-glare surface, and (iii) attaching the glass sheet to thefirst face of the metal sheet with a first interlayer.

The disclosure further relates to a method of manufacturing a laminatedstructure comprising: (i) providing a metal sheet including a first faceand a second face having a thickness ranging from about 0.1 mm to about5 mm extending between the first face and the second face, (ii)providing a glass sheet having a thickness of less than or equal toabout 2 mm, (iii) treating the glass sheet to produce at least oneanti-glare surface, (iv) optionally chemically strengthening the glasssheet, (v) optionally acid etching the glass sheet, and (vi) attachingthe glass sheet to the first face of the metal sheet with a firstinterlayer. In certain embodiments, the anti-glare treatment step may bechosen from acid etching, creamy etching, masked acid etching, sol gelprocessing, mechanical roughening, and combinations thereof. Accordingto other non-limiting embodiments, the chemical strengthening step maycomprise an ion exchange process.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from that description or recognized by practicing themethods described herein, including the detailed description whichfollows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description present various embodiments of thedisclosure, and are intended to provide an overview or framework forunderstanding the nature and character of the claims. The accompanyingdrawings are included to provide a further understanding, and areincorporated into and constitute a part of this specification. Thedrawings illustrate various non-limiting embodiments and together withthe description serve to explain the principles and operations of thedisclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

Various features, aspects and advantages of the present disclosure arebetter understood when the following detailed description is read withreference to the accompanying drawings wherein like structures areindicated with like reference numerals when possible, in which:

FIG. 1 is a schematic view of a cabinet incorporating a laminatedstructure in accordance with aspects of the disclosure;

FIG. 2 is a partial cross sectional view of the cabinet along line 2-2of FIG. 1 illustrating a laminated structure in accordance with aspectsof the disclosure;

FIG. 3 is another cross sectional view illustrating another examplelaminated structure in accordance with further aspects of thedisclosure;

FIG. 4 is a flow chart illustrating exemplary steps of manufacturinglaminated structures in accordance with aspects of the disclosure;

FIG. 5 is a schematic view illustrating the optional step of placing astack within a vacuum chamber and heating the stack to a laminationtemperature to produce the laminated structure in accordance withaspects of the disclosure;

FIG. 6 is a Weibull plot demonstrating impact energy at breakage for sixgroups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, 16 Gauge (1.59 mm)stainless steel, and various types of interlayers;

FIG. 7 is a Weibull plot demonstrating impact energy at breakage forfive groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, a layer of 0.38 mmpolyvinyl butyral, and various thicknesses of stainless steel;

FIG. 8 is a Weibull plot demonstrating impact energy at breakage forthree groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, a layer of 0.89 mmSentryGlas® ionomer, and various thicknesses of stainless steel;

FIG. 9 is a Weibull plot demonstrating impact energy at breakage forthree groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass compared to two groupsof fully tempered 4 mm Soda Lime glass;

FIG. 10 is a Weibull plot demonstrating impact energy at breakage fortwo groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, 0.38 mm polyvinylbutyral together with two alternative stainless steel sheets [i.e., 16Gauge (1.59 mm) and 24 Gauge (0.64 mm)] compared to another two groupsof laminated structures in accordance with aspects of the disclosureincluding acid-etched 1 mm Corning® Gorilla® glass, 0.38 mm polyvinylbutyral together with two alternative stainless steel sheets [i.e., 16Gauge (1.59 mm) and 24 Gauge (0.64 mm)];

FIG. 11 is a Weibull plot demonstrating impact energy at breakage fortwo groups of laminated structures in accordance with aspects of thedisclosure including acid-etched 0.7 mm Corning® Gorilla® glass, a layerof 0.89 mm SentryGlas® ionomer together with two alternative stainlesssteel sheets [i.e., 16 Gauge (1.59 mm) and 24 Gauge (0.64 mm)];

FIG. 12 is a Weibull plot demonstrating impact resistance for 1 mmcreamy etched anti-glare Corning® Gorilla® glass sheets at 10% and 40%haze levels under tension or compression as compared to 1 mm Corning®Gorilla® glass without anti-glare treatment; and

FIG. 13 is a Weibull plot demonstrating impact resistance for 1 mm solgel treated anti-glare Corning® Gorilla® glass sheets with 10% hazeunder tension or compression as compared to 1 mm Corning® Gorilla® glasswithout anti-glare treatment.

DETAILED DESCRIPTION

Laminated structures may be used in a wide range of applications inaccordance with aspects of the disclosure. For example, laminatedstructures may be used in various architectural applications such assiding, decorative panels, cabinet installations, wall coverings orother architectural applications. In further examples, the laminatedstructures may be used for furniture items and/or household appliances.For instance, the laminated structures may be incorporated as outerpanels of a cabinet or other furniture and/or household appliance. FIG.1 illustrates a schematic view of a cabinet 101 incorporating alaminated structure 103 in accordance with aspects of the disclosure. Inone non-limiting embodiment, the cabinet 101 can be incorporated in awall unit for storage. In another embodiment, the cabinet can berefrigerated. For instance, the cabinet 101 can comprise a refrigeratorand/or a freezer although various other non-refrigerated examples may bealternatively provided.

FIG. 2 illustrates an exemplary partial cross section along line 2-2 ofFIG. 1 wherein the laminated structure has been incorporated as an outerskin layer of a refrigerated cabinet (e.g., refrigerator and/orfreezer). The laminated structure 103 may comprise the entireconstruction in use although the laminated structure 103 may be combinedwith other elements of the panel, such as an insulating layer and/orinner skin depending on the particular application.

As shown in FIG. 2, the laminated structure can include a metal sheet201 that can comprise a wide range of metal types and/or a wide range ofthicknesses and configurations. For instance, the metal sheet 201 cancomprise steel, cold rolled steel, aluminum or any other suitable metal.In one non-limiting example, the metal sheet comprises stainless steel.Stainless steel may have suitable application for outer panelconstructions providing desired protection, resisting corrosion overtime and/or providing a desired outer appearance, such as a brushedstainless steel appearance.

The metal sheet 201 can include a first face 203 and a second face 205with a thickness T1 extending between the first face 203 and the secondface 205. The thickness T1 of the metal sheet 201 may vary depending onthe particular application. Relatively thin metal sheets may be used inapplications to reduce material costs and/or weight of the laminatedstructure while still providing sufficient resistance to deformation. Infurther embodiments, relatively thick metal sheets may be used inapplications where further support is required to maintain themechanical integrity of the laminated structure. In some embodiments,the thicknesses may range from a 25 Gauge metal sheet (e.g., about 0.5mm) up to a 12 Gauge metal sheet (e.g., about 2 mm). In furtherembodiments, the thicknesses may range from a 24 Gauge metal sheet(e.g., about 0.64 mm thick stainless steel) up to a 16 Gauge metal sheet(e.g., about 1.59 mm thick stainless steel). As such, referring to FIG.2, the thickness T1 of the metal sheet 201 may range from about 0.1 mmto about 5 mm, such as from about 0.5 mm to about 2 mm, or from about0.6 mm to about 1.6 mm, although other thicknesses may be provideddepending on the particular application.

As illustrated in FIG. 2, the laminated structure 103 can furtherinclude a chemically strengthened or non-chemically strengthened glasssheet 207 including a thickness T2 extending between a first face 209and a second face 211 of less than or equal to about 2 mm, such as lessthan or equal to 1.5 mm, such as from about 0.1 mm to about 1.1 mm, orfrom about 0.3 mm to about 1 mm. In one non-limiting embodiment, theglass sheet 207 has a thickness T2 of about 0.7 mm. In anotherembodiment, the glass sheet 207 has a thickness T2 of about 1 mm. In afurther embodiment, the glass sheet 207 has a thickness T2 of about 0.3mm. According to still further embodiments, the glass sheet 207 has athickness T2 ranging from about 0.3 mm to about 0.5 mm, or from about0.5 mm to about 1 mm. The glass sheet 207 may comprise, according tovarious embodiments, a glass such as an aluminosilicate glass, andalkali-aluminoborosilicate glass, or other glass material.

Various glass forming techniques may be used to produce glass sheets 207that may be incorporated within the laminated structure 103. Forinstance, fusion down draw techniques, fusion updraw techniques, slotdraw techniques or other processes may be used to provide a glass ribbonthat may be processed into glass sheets having the desired dimensionalconfiguration. For example, a fusion draw process can be provided toobtain a substantially pristine surface. In some embodiments, displayquality glass sheets 207 may be used to provide a transparent coveringover the first face 203 of the metal sheets 201. Providing displayquality glass can allow the aesthetic appearance of the first face 203of the metal sheets 201 to be preserved. At the same time, the glasssheet 207 can help maintain the pristine surface quality of the firstface 203 of the metal sheet 201. Indeed, scratches, smudging and/orother imperfections may be avoided by covering the metal sheet 201 withthe protective glass sheet 207.

In one embodiment, the glass sheets can comprise chemically strengthenedglass such as Corning® Gorilla® glass from Corning Incorporated. Suchchemically strengthened glass, for example, may be provided inaccordance with U.S. Pat. Nos. 7,666,511, 4,483,700, and 5,674,790,which are incorporated herein by reference in their entireties. Corning®Willow™ glass and Corning® EAGLE XG® glass from Corning Incorporated mayalso be suitable for use as the glass sheet in various embodiments.

Chemical strengthening may be carried out by an ion exchange process.For instance, a glass sheet (e.g., aluminosilicate glass,alkali-aluminoborosilicate glass) may be made by fusion drawing and thenchemically strengthening by immersing the glass sheet in a molten saltbath for a predetermined period of time. Ions within the glass sheet ator near the surface of the glass sheet are exchanged for larger metalions, for example, from the salt bath. The temperature of the moltensalt bath and treatment time period will vary; however, it is within theability of one skilled in the art to determine the time and temperatureaccording to the desired application. By way of non-limiting example,the temperature of the molten salt bath may range from about 430° C. toabout 450° C. and the predetermined time period may range from about 4to about 8 hours.

Without wishing to be bound by theory, it is believed that theincorporation of the larger ions into the glass strengthens the sheet bycreating a compressive stress in a near surface region. A correspondingtensile stress is induced within a central region of the glass sheet tobalance the compressive stress. The chemical strengthening process ofCorning® Gorilla® glass can have a relatively high compressive stress(e.g., from about 700 MPa to about 730 MPa; and even capable of greaterthan 800 MPa) at a relatively deep depth from the surface (e.g., about40 microns; and even capable of greater than 100 microns). Such glasscan have a high retained strength and high resistance to scratch damage,high impact resistance, and/or high flexural strength as well as asubstantially pristine surface. One exemplary glass composition maycomprise SiO₂, B₂O₃ and Na₂O, wherein (SiO₂+B₂O₃)≧66 mol. %, and Na₂O≧9mol. %.

In further embodiments, the chemically strengthened or non-chemicallystrengthened glass sheet 207 may be acid-etched to further strengthenthe glass sheet. The introduction of acid etching may enable use of eventhinner metal in the laminated structure of the disclosure withoutdeterioration in impact performance. The acid etching step, in someexamples, can remove from about 1.5 to about 1.7 microns from thesurfaces of the glass sheet 207.

Acid etching addresses the fact that glass strength is extremelysensitive to the size and the tip shape of surface flaws. By removingthe above-mentioned surface layer, it is believed that the acid etchingcan clear away a majority of surface flaws smaller than 1 micron. Whileacid etching may not remove larger flaws, the acid etching procedurewill tend to round the flaw tip which would otherwise dramaticallydecrease the stress concentration factor. The improvement in glasssurface (e.g., removal of small surface flaws and rounding the tips oflarger flaws) can dramatically increase glass strength, such as impactresistance. Moreover, only a relatively small depth of glass is removed,that will not result in significant compressive stress drop in the glasssheet which has relatively high compressive stress at a much largerdepth into the glass sheet such as 40 microns from the surface, or evengreater than 100 microns in some examples.

In one embodiment, the acid etching step can be conducted on ahorizontal spray etching system, with a chemical solution of about 1.5MHF/0.9M H₂SO₄. The other process parameters can include a processtemperature of about 90° F. (32.2° C.), process time of about 40seconds, spray pressure of about 20 psi, spray oscillation of about 15cycles per minute, and using approximately 0.48 gallon-per-minuteconical spray nozzles. However, it is possible to vary one or more ofthe above process parameters depending on the particular application andsuch variations are within the ability of one skilled in the art. Afteracid etching, the processed glass sheets may be cleaned with a rinsestep, e.g., using water. For example, approximately 0.3gallon-per-minute fanjet pattern nozzles may be used at a spray pressureof about 20 psi. The acid-etched glass sheets may then be dried. Forinstance, an air flow dryer system may be employed, such as an airturbine operating at approximately 5 hp.

As still further illustrated in FIG. 2, the laminated structure 103 canfurther include an interlayer 213 attaching the first glass sheet 207 tothe first face 203 of the metal sheet 201. The interlayer 213 can beformed from a wide range of materials depending on the application andcharacteristics of the glass sheet and metal sheet. According to certainembodiments, an optically clear interlayer can be provided that issubstantially transparent, although opaque and possibly coloredinterlayers may be provided in further examples. In further embodiments,desirable images can be printed, with either screen printing or digitalscanning printing, onto the glass side for aesthetic purposes or ontothe interlayer. Because these printed images can be arranged on theinterface (e.g., on the interlayer), they can be well preserved fromscratch damages during the product lifetime. In addition oralternatively, the interlayer may comprise a transparent layer to allowclear viewing of the outer surface of the metal sheets. Indeed, theinterlayer 213 can comprise a transparent interlayer 213 that providesan excellent optical interface between the glass sheet 207 and metalsheet 201. In some embodiments a display-quality glass sheet 207 may belaminated to the metal sheet 201 by the transparent interlayer 213 sothat the outer appearance of the first face 203 of the metal sheet 201may be easily viewed and preserved over time.

Still further, the interlayer 213 can be selected to help strengthen thelaminated structure 103 and can further help arrest glass pieces fromthe glass sheet 207 in the event that the glass sheet 207 shatters. Theinterlayer can comprise various materials such as ethylene vinyl acetate(EVA), thermoplastic polyurethane (TPU), Polyester (PET), acrylic (e.g.,acrylic pressure sensitive adhesive tape), polyvinyl butyral (PVB),SentryGlas® ionomer, or any other suitable interlayer material. If PETis used, in one embodiment, the PET material can be sandwiched betweentwo layers of acrylic adhesive material. In another non-limitingembodiment, the interlayer 213 can be selected to provide a Young'smodulus greater than or equal to 15 MPa. For instance, the interlayer213 may comprise polyvinyl butyral having a thickness ranging from about0.1 mm to about 0.8 mm, such as from about 0.3 mm to about 0.76 mm, suchas about 0.38 mm.

In a further embodiment, the interlayer 213 can comprise a Young'smodulus of greater than or equal to 275 MPa. For example, the firstinterlayer can include an ionomer with a Young's modulus of greater thanor equal to 275 MPa, such as about 300 MPa. In various embodiments, theionomer can comprise SentryGlas® ionomer available from DuPont. In suchembodiments, the thickness of the interlayer 213 can range, for example,from about 0.1 mm to about 2 mm, such as from about 0.5 mm to about 1.5mm, such as about 0.89 mm.

FIG. 3 illustrates another exemplary laminated structure 301 inaccordance with various aspects of the disclosure. The laminatedstructure 301 includes the interlayer 213 attaching the glass sheet 207to the first face 203 of the metal sheet 201. As shown, the laminatedstructure 301 can also include a second interlayer 303 attaching asecond glass sheet 305 to the second face 205 of the metal sheet 201.The second glass sheet 305 may, in certain embodiments, be a chemicallystrengthened glass sheet. The second interlayer 303 can, in certainembodiments, comprise the same material and have the same thickness T3as the first interlayer 213. Likewise, the second glass sheet 305, insome embodiments, can be identical to the first glass sheet 207including having the same thickness T2 and other features. Providing thelaminated structure 301 with a second glass sheet 305 can protect thesecond face of the metal sheet 201 in the same way the first glass sheet207 protects the first face 203 of the metal sheet 201.

With reference to FIG. 4, exemplary methods of manufacturing thelaminated structures 103 will now be described with the understandingthat similar or identical procedures maybe used to produce the laminatedstructures 301. The method begins with step 401 including providingand/or preparing the chemically strengthened or non-chemicallystrengthened glass sheet 207 (see column A), interlayer 213 (column B),and the metal sheet 201 (Column C). As described below, the methodconcludes with step 403 wherein the interlayer 213 attaches the glasssheet 207 to the first face 203 of the metal sheet 201.

As shown in FIG. 4, column A demonstrates optional steps that may becarried out during a step of providing the chemically strengthened ornon-chemically strengthened glass sheet 207. The method of providingand/or preparing the glass sheet 207 can include the step 405 ofproviding a glass sheet with a desired thickness (e.g., see T2 in FIG.2). As mentioned previously, the thickness T2 of the glass sheet 207 canbe less than equal to about 2 mm, such as less than or equal to 1.5 mm,such as from about 0.3 mm to about 1.1 mm, such as from about 0.5 mm toabout 1 mm. In one embodiment, the glass sheet 207 has a thickness T2 ofabout 0.7 mm. In another embodiment, the glass sheet 207 has a thicknessT2 of about 1 mm. In a further embodiment, the glass sheet 207 has athickness T2 of about 0.3 mm. The glass sheet 207 can comprise a glasssuch as an aluminosilicate glass, and alkali-aluminoborosilicate glass,or any other suitable glass material. The glass sheet 207 can beprovided by various techniques such as fusion down draw, fusion updraw,slot draw or other processes known in the art.

The glass sheet 207 may be optionally processed in step 406 so as toprovide the glass sheet 207 with at least one anti-glare surface.Anti-glare processing may take place before (step 406) or after (step412) the chemical strengthening step 411. For example, if the glasssheet 207 undergoes anti-glare processing before the chemicalstrengthening step 411, etching-based anti-glare processes can be used.Non-limiting processes are described, for example, in European PatentApplication Publication No. 2563733 A1 and International ApplicationPublication No. WO 2012/0749343 A1, which are incorporated herein byreference in their entireties. Suitable etching-based anti-glareprocesses include, but are not limited to, acid etching, creamy etching,masked acid etching, mechanical roughening (e.g., sand blasting), andcombinations thereof. In some non-limiting embodiments a combination ofmechanical roughening and acid etching is employed, although othercombinations are envisioned. According to various embodiments, theanti-glare processing may take place before and/or after theshaping/sizing step 407.

The method can then optionally proceed from step 405 or 406 to step 407of separating a plurality of glass sheets from a source glass sheet. Forexample, a glass ribbon of aluminosilicate glass oralkali-aluminoborosilicate glass may be formed from a fusion down drawprocess with the desired thickness. Then a plurality of glass sheets maybe cut from the glass ribbon and optionally further separated into asubset of glass sheets having the overall desired dimensions for theparticular application. Separating a plurality of glass sheets can becarried out with a wide range of techniques. For example, processing canbe selected to minimize adverse effects to glass strength due to itsrisk in introducing extra flaws, especially for thin glass. In oneexample, an approximately 3 mm diameter scoring wheel with a tip angleof about 110°, e.g., including diamond, may be used for the scoringoperation. Meanwhile, the applied force of approximately 0.8 kgf may beused for the scoring force.

The glass sheet having the desired size from step 407 may then befurther optionally processed during step 409. For instance, it may bedesirable to machine or otherwise finish at least one edge of the glasssheet 207 prior to the step of chemically strengthening the glass sheet207. For example, step 409 may include the step of edge grinding andfinishing to round or bevel the edge to the required profile to reducesharp edges, improve aesthetics and edge strength. In one embodiment, aprofiled diamond wheel of 400# (mesh size of diamond abrasive) may beused in a wide variety of applications. Other processing parameters caninclude a grinding speed ranging from about 10 m/sec to about 30 m/sec,a feed rate of about 0.5 m/min, and a grinding depth ranging from about0.1 mm to about 0.2 mm. If a higher edge strength is required, asubsequent grinding step may be carried out, for example, with an 800#diamond wheel. Such optional subsequent grinding step can includesimilar processing parameters, for example a grinding speed ranging fromabout 10 m/sec to about 30 m/sec, a feed rate of about 0.5 m/min, and agrinding depth ranging from about 0.05 mm to about 0.1 mm.

Once the desired size and properties are obtained and any edges aremachined or otherwise finished (e.g., during steps 406, 407, and/or409), the glass sheet may be chemically strengthened during step 411.For example, as discussed above, the chemical strengthening step maycomprise an ion exchange chemical strengthening technique used togenerate Corning® Gorilla® glass. Still further, the glass sheet 207 maybe optionally acid etched during step 413. Acid etching may be carriedout with exemplary procedures discussed above to further strengthen theglass sheets as desired for particular applications.

As discussed above, anti-glare processing may also be carried outsubsequent to the chemical strengthening step 411. For example, in step412, the strengthened glass sheet 207 may be subjected to sol gelprocessing to produce at least one anti-glare surface. Non-limiting solgel processes are described, for example, in European Patent No. 1802557B1, which is incorporated herein by reference in its entirety. Suitablesol gel-based anti-glare processes may also include, for example,coating the glass sheet 207 with an anti-glare sol gel composition andbaking the sheet at relatively low temperature (e.g., less than about350° C.). According to various embodiments, subsequent to sol gelanti-glare processing, the glass sheet 207 can then be further processedby acid etching in step 413.

Optionally, before entering the lamination block 403 of the method formanufacturing, the glass sheet may be cleaned during step 415. Cleaningmay be designed to remove surface dirt, stains, and other residues. Theglass cleaning step can be conducted with an industrial ultrasoniccleaner, a horizontal spray system or other cleaning technique.

Many of the steps of column A are optional and may be even excludedaltogether. For instance the chemically strengthened or non-chemicallystrengthened glass sheet may simply be provided for the process oflaminating. Moreover, various steps are optional and may be excludedaltogether. For example, after the step 405, the glass sheet may alreadyinclude the desired thickness as well as the desired dimensions. In suchan example, the method may proceed directly from step 405 to step 409 ormay even proceed directly to step 411. If the provided glass sheetalready exhibits the desired strength properties, the chemicalstrengthening step 411 and/or the acid etching step 413 may be skipped.Moreover, if the glass sheet is sized during step 407, the edgecharacteristics may be sufficient for the particular application,wherein the method may proceed directly to step 411 without machiningthe edges during step 409. As further illustrated in column A, the stepof cleaning 415 can also be skipped depending on the particularapplication. Finally, if the glass sheet is processed in step 406 toproduce at least one anti-glare surface, then step 412 can be skipped,or vice versa.

The providing and/or preparing block 401 can further include providingand/or preparing the interlayer 213 (column B). For instance, the methodcan include the step 417 of providing the interlayer. The interlayer canbe provided, by way of non-limiting example, as polyvinyl butyral (PVB)or a SentryGlas® ionomer interlayer although other interlayer types maybe provided in further examples as discussed above. In one embodiment,the interlayer 213 can comprise PVB with a thickness ranging from about0.1 mm to about 0.8 mm, such as from about 0.3 mm to about 0.76 mm, suchas about 0.38 mm. In another embodiment, the interlayer 213 can compriseSentryGlas® ionomer with a thickness ranging from about 0.1 mm to about2 mm, such as from about 0.5 mm to about 1.5 mm, such as about 0.89 mm.

In various embodiments, the method can continue to step 419 of cuttingthe interlayer to the appropriate size for the laminated structure.Still further, the interlayer may be conditioned, for example, tocontrol the moisture content of the interlayer. In one example, the step421 of conditioning adjusts the moisture content of the interlayer toless than about 1%, such as less than or equal to about 0.65%, such asless than or equal to about 0.2%. Controlling the moisture content ofthe interlayer may be beneficial to help achieve excellent bondingquality of the interlayer during the lamination procedure. In otherembodiments, if the interlayer comprises PVB, the moisture content maybe controlled to be less than or equal to about 0.65%. If SentryGlas®ionomer is used, the moisture content may be controlled to be less thanor equal to about 0.2% according to certain embodiments. Controlling themoisture content can be carried out in various ways known in the art.For example, the interlayer may be placed in a controlled environmentwhere the temperature and/or humidity are adjusted to achieve thedesired moisture content of the interlayer.

As shown in column B, steps of providing and/or preparing the interlayer213 may be carried out in different orders and/or certain steps may beomitted altogether. For example, the interlayer may be provided with theappropriate size. In such examples, the step 419 of cutting may beomitted. Furthermore, the step of conditioning may be omitted in furtherexamples or may be carried out without the step of cutting or prior tothe step of cutting as shown in FIG. 4.

The providing and/or preparing block 401 can further include providingand/or preparing the metal sheet 201 (column C). The method can beginwith step 423 of providing the metal sheet 201 including a first face203 and a second face 205 with the desired thickness extending betweenthe first face 203 and the second face 205. In one embodiment, the metalsheet 201 can be provided as a stainless steel metal sheet 201 althoughother materials can be used in further embodiments. In anotherembodiment, the stainless steel metal sheet 201 may range from a 25Gauge metal sheet (e.g., about 0.5 mm) up to a 12 Gauge metal sheet(e.g., about 2 mm). In further examples, the thicknesses may range froma 24 Gauge metal sheet (e.g., about 0.64 mm thick stainless steel) up toa 16 Gauge metal sheet (e.g., about 1.59 mm thick stainless steel). Assuch, the thickness T1 of the metal sheet 201 can range from about 0.1mm to about 5 mm, such as from about 0.5 mm to about 2 mm, or from about0.64 mm to about 1.59 mm, although other thicknesses may be provideddepending on the particular application.

The method can further proceed from the step 423 of providing the metalsheet 201 to the step 425 of cutting or otherwise shaping the metalsheet 201 to including the appropriate dimensions. In one example, lasercutting may be employed to minimize edge deformation that wouldotherwise affect bonding quality of the interlay and glass sheet at theedge of the metal sheet 201.

After step 425, the method can optionally proceed to step 427 of edgetrimming and cleaning. For example, after the cut, the edge of thestainless steel sheet may be trimmed by a mechanical milling orbroaching method, and cleaned with a clean wiper and/or isopropanol orother suitable solvent. The steel surface can also be cleaned with aTeknek (or equivalent) tacky roller to remove surface dust andparticulates. The method can then proceed to step 429 of removing anyprotective film from the steel sheet. For example, the front and backprotective films can be removed prior to lamination. As shown, steps425, 427 and 429 are optional wherein any one of the steps may beomitted and/or the steps may be carried out in various orders asillustrated.

After the glass sheet 207, interlayer 213 and metal sheet 201 areprovided and/or prepared under the providing/preparing block 401, themethod can then proceed to the lamination block 403 including the stepof attaching the glass sheet 207 to the first face 203 of the metalsheet 201 with a first interlayer 213 to provide the laminated structure103 illustrated in FIG. 2. Likewise, the lamination block 403 may alsoinclude the step of attaching a second glass sheet 305 to the secondface 205 of the metal sheet 201 with a second interlayer 303 to providethe laminated structure 301 shown in FIG. 3.

Under the lamination block 403, the method can begin by step 431 ofbuilding a stack with the interlayer 213 placed between the glass sheet207 and the first face 203 of the metal sheet 201 to provide a 3-layerstack (e.g., see FIG. 2). In addition, if desired, the method cancontinue to build the stack with the second interlayer 303 placedbetween the second glass sheet 305 and the second face 205 of the metalsheet 201 to provide a 5-layer stack (e.g., see FIG. 3). The stack 501can then be optionally secured to prevent shifting, for example, byplacing pieces of high-temperature polyester tape on at least two edges.

The glass sheet 207 may be attached to the metal sheet 201 using theinterlayer 213 by any means known in the art. For instance, as shown inFIG. 5, the stack 501 can then be placed within a vacuum chamber, suchas a vacuum bag 503. In the step of vacuum bagging, these assembledparts may be wrapped in thin breather cloth which is secured by tape(e.g., polyester tape), then wrapped in looser breather material andplaced within a plastic film lamination bag. The parts may be arrangedin a single layer within the bag, or multiple stacks may be processed atone time for higher throughput. The bag can be heat sealed with a vacuumport attached. The port of the vacuum bag may be attached to a vacuumhose within an autoclave chamber 505 and vacuum may be applied with thechamber still open to check for leaks. Other bagged parts may be loadedas well, up to the part capacity of the autoclave 505.

As shown in step 433, the vacuum chamber 503 can then be at leastpartially evacuated and the stack can be heated with a predeterminedtemperature and pressure profile. For example, the thermal processingstep may be carried out with an autoclave wherein specific temperatureand pressure profiles are used in order to achieve preferred adhesion(bonding) quality of the laminated structure.

For laminated structures with a PVB interlayer, the parts are placedunder vacuum within the sealed bag and subjected to an appropriatetemperature and pressure profile. For instance, the temperature may beramped to the soak temperature of about 130° C. (266° F.) at a rate ofapproximately 3° F./minute. When the temperature setpoint is reached, apressure ramp of about 5 psi/minute is initiated until the pressuresetpoint of about 80 psi is reached. After a soak time of about 30minutes, the temperature is ramped back down at a rate of approximately3° F./minute. Pressure is held at about 80 psi until the temperaturereaches about 50° C. (122° F.) to minimize bubble formation in the PVB,at which point the pressure is also ramped down at a rate of about 5psi/minute. After the chamber has cooled and pressure equilibrium isestablished, the parts are removed from the autoclave, the bagging,breather cloth, and tape is removed, and the parts cleaned of laminationresidues.

For glass/steel laminates with a SentryGlas® ionomer interlayer, a cyclesimilar to that detailed above for PVB may be used. For instance, thetemperature may be ramped to about 133° C. (272° F.) at a ramp rate ofabout 4° F./minute. After a soak time of about 60 minutes, the ramp ratecan be ramped down at a rate of about 4° F./minute until the temperaturereaches 210° F. to minimize haze formation in the film. The laminatedstructure 103, 301 is then provided at the end of the process designatedby 435 in FIG. 4.

Still further aspects of the disclosure can include optional processingtechniques for use during a method of manufacturing the laminatedstructure that may provide further beneficial features to the laminatedstructure. For example, processing techniques can optionally includepreparation steps for the glass sheet including a scoring and breakingstep, edge finishing, ion exchange to apply the compressive surfacelayer and acid etching to further reduce glass surface flaws. In furtherembodiments, optional processing techniques can include decoration ofthe glass or other components to provide the glass with a decoratedappearance. For the interlayer, processing techniques can optionallyinclude proper conditioning of the interlayer (e.g., PVB or SentryGlas®ionomer) interlayer to improve bonding strength. For the steel layer,processing techniques can optionally include laser cutting so as toavoid the edge deformation caused by mechanical methods. During the stepof lamination, the present disclosure can further include the step ofvacuum applied thermal processing with the specific thermal cyclingprofiles that may be customized for various interlayers (e.g., PVB andSentryGlas® ionomer interlayers), for the purpose of improved bondingstrength and reduced air bubbles.

Further optional processing steps may include providing the laminatedstructures with integrated mounting features, such as holes and/orhooks, which may facilitate installation during end product use. Forinstance, mounting brackets may be attached to the metal sheet orotherwise provided on the laminated structure. In certain embodiments,the metal sheet may be machined so as to incorporate the holes and/orhooks or any other suitable mounting features.

In another embodiment, the laminated structures may be manufactured soas to reduce or eliminate the occurrence of glass edge contact. Edgecontact, especially during the process of handling glass panels, is oneof the main causes of glass panel breakage either during installation oruse of the laminated structure. In certain cases, edge contact mayinduce latent defects and/or edge chipping and/or edge cracks on theglass layer. Thus, according to various embodiments disclosed herein,the laminated substrate may be assembled so as to protect the glassedges, e.g., by providing a metal sheet which wraps around the outeredges of the glass sheet. In some embodiments, the glass sheet may benested inside the recess created by the metal sheet. Otherconfigurations are also envisioned which can reduce the potential forcontact with the outer edges of the glass sheet and therefore reduce oravoid the mechanical degradation of the laminated structure.

In various embodiments, an anti-microbial coating can be applied to thesurface of the glass sheet. In other embodiments, the glass sheet caninclude a composition having anti-microbial characteristics. Forexample, the glass sheet can be a glass or glass ceramic materialcontaining silver, copper or a combination of silver and copper.Exemplary compositions include, but are not limited to, silver andcopper, or mixture thereof, which may be zero valent existing in theglass or glass ceramic as Ag⁰ or Cu⁰, which is the metallic form; can beionic and exist in the glass or glass ceramic as Ag⁺¹, Cu⁺¹ or Cu⁺²; orcan be in the glass or glass ceramic as a mixture of the zero valent andionic forms of one or both agents, for example, Ag⁰ and Cu⁺¹ and/orCu⁺², Ag⁺¹ and Cu⁰, and other combination of the zero valent and ionicspecies. The antimicrobial agent can be incorporated into the glass orglass ceramic by either (1) ion-exchange of a preformed GC using anion-exchange bath containing one or both of the foregoing antimicrobialagents, or (2) by including one or both of the foregoing antimicrobialagents into batched materials used to prepare a glass that is thencerammed to form a glass or glass ceramic. In (1), the antimicrobialagent will be present in the glass or glass ceramic in ionic form, asthe oxide, since nitrates of the antimicrobial agent can be used for theion-exchange and because the nitrate species on the glass or glassceramic are easily decomposed during the ion-exchange process.Additional anti-microbial coatings and compositions are described inWO2013/036746, entitled, “Antimicrobial Composite Material,” U.S.application Ser. No. 13/649,499, entitled “AntimicrobialGlass-Ceramics,” U.S. application Ser. No. 13/197,312, entitled “Coated,Antimicrobial, Chemically Strengthened Glass and Method of Making,” andU.S. application Ser. No. 14/176,470 entitled, “Antimicrobial GlassArticles and Methods of Making and Using Same,” the entirety of eachbeing incorporated herein by reference.

As described above, laminated structures can comprise a metal sheetincluding a first face and a second face with a thickness ranging fromabout 0.1 mm to about 5 mm extending between the first face and thesecond face. The laminated structures can further include a firstchemically strengthened or non-chemically strengthened glass sheetincluding a thickness of less than or equal to about 2 mm. The laminatedstructures can still further include a first interlayer attaching thefirst glass sheet to the first face of the metal sheet. In illustrativeexamples, the laminated structures can comprise: 1) at least one layerof thin Corning® Gorilla® glass (e.g., with a thickness of about 0.7 mmor about 1.0 mm) or Corning® Willow™ glass (e.g., with a thickness ofabout 0.3 mm or less) as the outermost surface, 2) at least one layer ofpolymer interlayer (0.38 mm Polyvinyl butyral (PVB) or 0.89 mmSentryGlas® ionomer), and 3) a layer of stainless steel (e.g., rangingfrom 24 Gauge to 16 Gauge, about 0.635 mm to 1.59 mm).

Laminated structures of the present disclosure may have a number ofadvantages over fully tempered soda lime and stainless steel. Forexample, laminated structures of the present disclosure may exhibiteither comparable or superior performance in terms of impact resistanceover the fully tempered soda lime mono-layers (as thick as 4 mm). Inaddition, the laminated structures of the present disclosure may be ableto retain glass fragments in place if they break, as compared to fullytempered soda lime which releases glass chips to the surroundingenvironment if broken. Compared to stainless steel monolithicstructures, the presence of a glass layer in the laminated structures ofthe present disclosure may enable higher structure hardness andtherefore higher scratch resistance, and may help maintain the freshaesthetic look of the steel surface over a longer period of time.

Advantages of some exemplary embodiments of the disclosure can producehigh quality laminated structures with one or two layers of relativelythin glass (e.g., less than or equal to 2 mm). Moreover, by use ofvarious processing techniques for stainless steel laminatedapplications, the laminated structures may have the ability to maintainthe aesthetic look of brushed stainless steel during a longer servicetime. Moreover, laminated structures of the present disclosure maycircumvent typical issues of low impact resistance caused by “localizeddeformation” that might otherwise occur with other laminate structureswith a relatively thin glass layer. In addition, exemplary laminatedstructures strengthened by acid etching may enable the use of thinnersteel like 24 Gauge (0.635 mm) for glass/steel laminates without asubstantial adverse effect on impact resistance.

As such, the disclosure further presents laminated structures thatprotect a metal sheet with a glass sheet to avoid scratching of themetal sheet and soiling the surface of the glass sheet. Indeed, smudgesor dirt may be easily removed from the surface of the glass sheet in aconvenient manner that may be more difficult to remove from anunprotected metal surface. In some examples, the glass sheet can belaminated to a stainless steel metal sheet to provide an attractivesurface that has enhanced scratch resistance, and is relatively easy toclean, for example, with respect to fingerprints, oil smudges, microbialcontaminants, etc. According to various embodiments, the glass sheet mayalso be treated to provide an anti-glare surface to provide thelaminated structure with further aesthetic benefits. The glass sheet canthereby help preserve the aesthetic look of the stainless steel and canhelp facilitate cleaning and maintenance of the surface of the laminatedstructure.

Moreover, the glass sheet of the laminated structure can provide thestainless steel metal sheet with increased resistance to plasticdeformation under sharp impact. As such, the glass sheet may help toshield the metal sheet from impacts that may otherwise dent or damagethe metal sheet. The glass sheet may also increase thechemical/electrochemical stability when compared to a stainless steelmetal sheet, thereby preserving the surface characteristics of thestainless steel.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the present disclosurewithout departing from the spirit and scope of the disclosure. Sincemodifications combinations, sub-combinations and variations of thedisclosed embodiments incorporating the spirit and substance of thedisclosure may occur to persons skilled in the art, the disclosureshould be construed to include everything within the scope of theappended claims and their equivalents.

The following Examples are intended to be non-restrictive andillustrative only, with the scope of the invention being defined by theclaims.

Examples Laminated Glass/Metal Structures

FIGS. 6-11 show test results performed on various laminated structuresto illustrate performance characteristics. In each test, a four inchsquare laminated structure was placed on a 1 inch thick flexible foamsupport with the glass sheet facing upwards. A 535 gram ball was thendropped at varying heights from the glass sheet. Once breakage wasnoted, the energy corresponding to the height of the ball was recorded.The Weibull plots illustrated in FIGS. 6-11 were created by plotting thepercent failure vs. the energy at failure. As such, in each plot, theY-axis (i.e., vertical axis) has the units of percent (%) while theX-axis (i.e., horizontal axis) has the units of Joules (i.e., the energyat failure).

FIG. 6 is a Weibull plot demonstrating impact energy at breakage for sixgroups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, 16 Gauge (1.59 mm)stainless steel, and various types of interlayers. Data set 601represents a laminated structure including an interlayer comprisingSentryGlas® ionomer with a thickness of 0.89 mm. Data set 603 representsa laminated structure with an interlayer comprising polyvinyl butyral(PVB) with a thickness of 0.38 mm. Data set 605 represents a laminatedstructure with an interlayer comprising SentryGlas® ionomer with athickness of 1.5 mm. Data set 607 represents a laminated structure withan interlayer comprising thermoplastic polyurethane (TPU) with athickness of 0.34 mm. Data set 609 represents a laminated structure withan interlayer comprising acrylic pressure sensitive adhesive tape(hereinafter “APSAT”) with a thickness of 0.05 mm. Data set 611represents a laminated structure with an interlayer comprisingAPSAT+PET+APSAT with a thickness of 0.17 mm. The APSAT+PET+APSATinterlayer comprises a PET film in the middle of the laminate that issandwiched between two layers of APSAT. Data set 613 is a comparativesample for comparison purposes with the six other groups 601, 603, 605,607, 609, and 611 of laminated structures in accordance with aspects ofthe disclosure. Data set 613 comprises a fully tempered soda lime glasssheet with a thickness of 4 mm. The data represented by the data setsshown in FIG. 6 is reproduced in Table 1 below wherein the samples ineach set are sorted in ascending order of impact energy:

TABLE 1 609 611 601 603 605 607 APSAT APSAT + PET + 613 Sample SG0.89PVB0.38 SG1.5 TPU0.34 0.05 APSAT SL4 mm 1 2.24 3.03 2.24 2.24 2.25 1.983.28 2 4.87 3.56 2.50 2.24 2.25 1.98 3.54 3 4.87 3.56 2.76 2.24 2.252.25 3.54 4 5.39 3.82 2.76 2.51 2.51 2.25 3.81 5 5.39 3.82 2.76 2.772.77 2.25 3.81 6 5.91 4.08 2.76 2.77 2.77 2.51 3.81 7 6.18 4.08 2.762.77 2.77 2.77 4.07 8 6.44 4.08 2.76 2.77 2.77 2.77 4.07 9 6.70 4.083.29 3.03 2.77 2.77 4.33 10 7.23 4.08 3.55 3.03 2.77 3.30 4.33 11 7.234.08 3.55 3.03 3.03 3.30 4.59 12 7.49 4.08 3.55 3.03 3.03 3.56 4.59 137.49 4.08 3.81 3.29 3.03 3.82 4.86 14 7.49 4.08 3.81 3.29 3.03 4.61 4.8615 7.49 4.08 4.07 3.29 3.30 4.86 16 7.49 4.34 4.34 3.29 3.30 4.86 177.49 4.34 4.34 3.29 3.30 4.86 18 7.49 4.34 4.34 3.29 3.30 5.12 19 7.494.34 4.60 3.29 3.30 5.12 20 7.49 4.34 5.12 3.29 3.30 5.38 21 4.60 5.123.29 3.30 5.38 22 4.60 5.12 3.56 3.56 5.38 23 4.60 5.65 3.56 3.56 5.6424 4.60 5.91 3.56 3.56 5.90 25 4.60 6.17 3.82 3.56 5.90 26 4.87 6.704.08 3.82 27 5.13 6.70 4.08 3.82 28 5.65 6.70 4.34 3.82 29 6.18 6.964.60 3.82 30 7.48 4.60 3.82

Data sets 605, 607, 609, and 611 of the Weibull plot of FIG. 6 show thatthe laminated structures with APSAT, TPU, and 1.5 mm SentryGlas® ionomerdo not have comparable impact resistance with a 4 mm sheet of fullytempered soda lime glass represented by data set 613. On the other hand,the laminated structures with 0.38 mm PVB represented by data set 603 iscomparably impact-resistant, and the group with 0.89 SentryGlas® ionomerrepresented by data set 601 has a superior impact resistance, which ismuch higher than all other data sets 603, 605, 607, 609, and 611 and thesoda lime 613. Comparing data sets 601 and 605, it is recognized thatimpact resistance increased with decreased thickness of the SentryGlasPlus® ionomer interlayer.

FIG. 7 is a Weibull plot demonstrating impact energy at breakage forfive groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, a layer of 0.38 mmpolyvinyl butyral (PVB), and various thicknesses of stainless steelsheets. Data set 701 represents a laminated structure including a 16Gauge stainless steel sheet (i.e., 1.59 mm thick). Data set 703represents a laminated structure including an 18 Gauge stainless steelsheet (i.e., 1.27 mm thick). Data set 705 represents a laminatedstructure including a 20 Gauge stainless steel sheet (i.e., 0.95 mmthick). Data set 707 represents a laminated structure including a 22Gauge stainless steel sheet (i.e., 0.79 mm thick). Data set 709represents a laminated structure including a 24 Gauge stainless steel(i.e., 0.64 mm thick). The data represented by the data sets shown inFIG. 7 is reproduced in Table 2 below wherein the samples in each setare sorted in ascending order of impact energy:

TABLE 2 701 703 705 707 709 Gauge Gauge Gauge Gauge Gauge Sample 16 1820 22 24 1 3.03 2.25 1.992 1.73 1.99 2 3.56 2.78 1.992 1.99 2.26 3 3.563.30 2.254 2.25 2.52 4 3.82 3.56 2.254 2.25 2.52 5 3.82 3.82 2.516 2.252.52 6 4.08 3.82 2.516 2.25 2.52 7 4.08 4.09 2.516 2.52 2.52 8 4.08 4.092.778 2.52 2.52 9 4.08 4.09 3.040 2.52 2.78 10 4.08 4.35 3.040 2.78 3.0411 4.08 4.61 3.302 3.04 3.04 12 4.08 4.61 3.564 3.04 3.30 13 4.08 4.873.564 3.30 3.30 14 4.08 5.14 3.827 3.57 3.83 15 4.08 5.40 4.875 3.574.09 16 4.34 17 4.34 18 4.34 19 4.34 20 4.34 21 4.60 22 4.60 23 4.60 244.60 25 4.60 26 4.87 27 5.13 28 5.65 29 6.18

As noted, the three groups of laminates with thinner stainless steelsheet thicknesses (i.e., Gauge 20, Gauge 22, and Gauge 24 thicknesses)cannot achieve as high impact resistance as the two groups with thickerstainless steel sheet thicknesses (i.e., Gauge 16 and Gauge 18thicknesses).

FIG. 8 is a Weibull plot demonstrating impact energy at breakage forthree groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, a layer of 0.89 mmSentryGlas® ionomer, and various thicknesses of stainless steel sheets.Data set 801 represents a laminated structure including a 16 Gaugestainless steel sheet (i.e., 1.59 mm thick). Data set 803 represents alaminated structure including a 22 Gauge stainless steel sheet (i.e.,0.79 mm thick). Data set 805 represents a laminated structure includinga 24 Gauge stainless steel (i.e., 0.64 mm thick). The data representedby the data sets shown in FIG. 8 is reproduced in Table 3 below whereinthe samples in each set are sorted in ascending order of impact energy:

TABLE 3 801 803 805 Sample Gauge 16 Gauge 22 Gauge 24 1 2.24 2.77 1.73 24.87 3.04 2.25 3 4.87 3.30 2.78 4 5.39 3.30 3.30 5 5.39 4.35 3.30 6 5.914.35 3.30 7 6.18 4.61 3.56 8 6.44 4.87 3.56 9 6.70 5.13 3.56 10 7.235.40 3.56 11 7.23 5.66 3.82 12 7.49 5.92 4.09 13 7.49 6.44 4.09 14 7.496.71 4.35 15 7.49 7.49 4.61 16 7.49 17 7.49 18 7.49 19 7.49 20 7.49

As these data show, the presence of 0.89 mm SentryGlas® ionomer providesimpressive impact resistance. Indeed, as shown by data set 803, even thelaminated structures with a thinner steel layer (as thin as 0.79 mm)reaches a comparable impact resistance with the fully tempered 4 mm SodaLime (see data set 613 in FIG. 6) or the laminated structures with 1 mmGorilla glass plus 0.38 PVB plus 1.59 mm steel (see data set 603 in FIG.6). As shown by data set 801, laminate structures with 1.59 mm stainlesssteel and 0.89 mm SentryGlas® ionomer has the highest impact resistance.

FIG. 9 is a Weibull plot demonstrating impact energy at breakage forthree groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass compared to two groupsof fully tempered 4 mm Soda Lime glass. Data set 901 represents alaminated structure including a 16 Gauge stainless steel sheet (i.e.,1.59 mm thick) with a PVB interlayer having a thickness of 0.38 mm. Dataset 903 represents a laminated structure including a 16 Gauge stainlesssteel sheet (i.e., 1.59 mm thick) with a 0.89 mm SentryGlas® ionomer asthe interlayer. Data set 905 represents a laminated structure includinga 22 Gauge stainless steel sheet (i.e., 0.79 mm thick) with a 0.89 mmSentryGlas® ionomer as the interlayer. For comparison purposes, two setsof soda lime glass where added. Data set 907 represents fully temperedsoda lime glass with a thickness of 4 mm. Data set 909 represents fullytempered soda lime glass with a thickness of 4 mm with a black fritcoating added. The data represented by the data sets shown in FIG. 9 isreproduced in Table 4 below wherein the samples in each set are sortedin ascending order of impact energy:

TABLE 4 901 903 905 909 PVB0.38 SG0.89 SG0.89 907 FT SL4 Steel SteelSteel SL4 mm Sample 1.59 1.59 0.79 mm w/Frit 1 3.03 2.24 2.77 3.28 1.452 3.56 4.87 3.04 3.54 1.71 3 3.56 4.87 3.30 3.54 1.71 4 3.82 5.39 3.303.81 1.71 5 3.82 5.39 4.35 3.81 1.71 6 4.08 5.91 4.35 3.81 1.97 7 4.086.18 4.61 4.07 1.97 8 4.08 6.44 4.87 4.07 1.97 9 4.08 6.70 5.13 4.331.97 10 4.08 7.23 5.40 4.33 1.97 11 4.08 7.23 5.66 4.59 1.97 12 4.087.49 5.92 4.59 1.97 13 4.08 7.49 6.44 4.86 1.97 14 4.08 7.49 6.71 4.861.97 15 4.08 7.49 7.49 4.86 2.23 16 4.34 7.49 4.86 2.23 17 4.34 7.494.86 2.23 18 4.34 7.49 5.12 2.23 19 4.34 7.49 5.12 2.50 20 4.34 7.495.38 2.76 21 4.60 5.38 22 4.60 5.38 23 4.60 5.64 24 4.60 5.90 25 4.605.90 26 4.87 27 5.13 28 5.65 29 6.18

FIG. 10 is a Weibull plot demonstrating impact energy at breakage fortwo groups of laminated structures in accordance with aspects of thedisclosure including 1 mm Corning® Gorilla® glass, 0.38 mm polyvinylbutyral (PVB) together with two alternative stainless steel sheets. Dataset 1005 represents 16 Gauge (1.59 mm) stainless steel sheet and dataset 1007 represents 24 Gauge (0.64 mm) stainless steel sheet. FIG. 10further shows impact energy at breakage for two groups of laminatedstructures in accordance with aspects of the disclosure includingacid-etched 1 mm Corning® Gorilla® glass, 0.38 mm polyvinyl butyral(PVB) together with two alternative stainless steel sheets. Data set1003 represents 16 Gauge (1.59 mm) stainless steel sheet and data set1001 represents 24 Gauge (0.64 mm) stainless steel sheet. Forcomparative purposes, data set 1009 represents fully tempered soda limeglass sheet with a thickness of 4 mm. The data represented by the datasets shown in FIG. 10 is reproduced in Tables 5a and 5b below whereinthe samples in each set are sorted in ascending order of impact energy:

TABLE 5a 1001 1003 1005 1007 F_GG1 F_GG1 IOXed_GG1 IOXed_GG1 1009 GaugeGauge Gauge Gauge SL4 Sample 24 16 16 24 mm 1 4.34 4.34 2.51 1.99 3.28 24.60 5.39 2.77 2.26 3.54 3 5.65 5.91 2.77 2.52 3.54 4 5.65 6.70 3.032.52 3.81 5 6.96 6.96 3.56 2.52 3.81 6 7.23 7.49 3.56 2.52 3.81 7 7.497.49 3.82 2.52 4.07 8 7.49 7.49 3.82 2.52 4.07 9 7.49 7.49 3.82 2.784.33 10 7.49 7.49 3.82 3.04 4.33 11 7.49 7.49 3.82 3.04 4.59 12 7.497.49 3.82 3.30 4.59 13 7.49 7.49 4.08 3.30 4.86 14 7.49 7.49 4.08 3.834.86 15 7.49 7.49 4.08 4.09 4.86 16 7.49 7.49 4.08 4.86 17 7.49 7.494.08 4.86 18 4.08 5.12 19 4.08 5.12 20 4.08 5.38

TABLE 5b 1001 1003 1005 1007 F_GG1 F_GG1 IOXed_GG1 IOXed_GG1 1009 GaugeGauge Gauge Gauge SL4 Sample 24 16 16 24 mm 21 4.08 5.38 22 4.08 5.38 234.08 5.64 24 4.08 5.90 25 4.34 5.90 26 4.34 27 4.34 28 4.34 29 4.34 304.60 31 4.60 32 4.60 33 4.60 34 4.60 35 4.60 36 4.60 37 4.87 38 5.13 395.39 40 5.65 41 5.65 42 5.91 43 6.18 44 7.23

As demonstrated by data sets 1001 and 1003, both acid-etched Corning®Gorilla® glass laminated structures have superior impact performancewhen compared to non-acid treated chemically strengthened glasslaminated structures and when compared to 4 mm soda lime glass.

FIG. 11 is a Weibull plot demonstrating impact energy at breakage fortwo groups of laminated structures in accordance with aspects of thedisclosure including acid-etched 0.7 mm Corning® Gorilla® glass, a layerof 0.89 mm SentryGlas® ionomer together with two alternative stainlesssteel sheets. Data set 1103 represents 16 Gauge (1.59 mm) stainlesssteel sheet. Data set 1101 represents 24 Gauge (0.64 mm) stainless steelsheet. For comparative purposes, data set 1105 represents fully temperedsoda lime glass sheet with a thickness of 4 mm. The data represented bythe data sets shown in FIG. 11 is reproduced in Table 6 below whereinthe samples in each set are sorted in ascending order of impact energy:

TABLE 6 1101 1103 1105 F_GG07 F_GG07 SL4 Sample Gauge 24 Gauge 16 mm 14.60 5.91 3.28 2 5.91 7.49 3.54 3 6.18 7.49 3.54 4 7.49 7.49 3.81 5 7.497.49 3.81 6 7.49 7.49 3.81 7 7.49 7.49 4.07 8 7.49 7.49 4.07 9 7.49 7.494.33 10 7.49 7.49 4.33 11 7.49 7.49 4.59 12 7.49 7.49 4.59 13 7.49 7.494.86 14 7.49 7.49 4.86 15 7.49 7.49 4.86 16 7.49 7.49 4.86 17 7.49 4.8618 5.12 19 5.12 20 5.38 21 5.38 22 5.38 23 5.64 24 5.90 25 5.90

FIG. 11 demonstrates that thinner sheets of glass comprising acid-etched0.7 mm Corning® Gorilla® glass used in a laminated structure can be usedwith thin sheets of steel (e.g., 24 Gauge—0.64 mm thick stainless steel)with a layer of 0.89 mm SentryGlas® ionomer and still achieve superiorimpact performance when compared to 4 mm soda lime glass. As such, theexperimental results demonstrate that acid-etched Corning® Gorilla®glass indeed has the ability to enable the use of thinner steel (like 24Gauge) for the construction of highly impact resistant glass/steellaminates, even with 0.7 mm Gorilla® glass.

Glass Sheets with Anti-Glare Function

FIGS. 12 and 13 show test results performed on various glass sheets toillustrate strength performance characteristics. In each test, a fourinch square glass sheet having a thickness of 1 mm was placed on a 1inch thick flexible foam support. A 128 gram ball was then dropped atvarying heights from the glass sheet. Once breakage was noted, theheight of the ball was recorded. The Weibull plots illustrated in FIGS.12 and 13 were created by plotting the percent failure vs. the height ofthe ball at failure. As such, in both plots, the Y-axis (i.e., verticalaxis) is expressed in units of (%) while the X-axis (i.e., horizontalaxis) is expressed in units of (cm).

FIG. 12 is a Weibull plot demonstrating impact resistance for creamyetched anti-glare glass sheets at 10% and 40% haze levels under tensionor compression as compared to Corning® Gorilla® glass without anti-glaretreatment. Data set 1201 represents a 1 mm thick creamy etchedanti-glare Corning® Gorilla® glass sheet with 10% transmission hazeunder tension. Data set 1203 represents a 1 mm thick creamy etchedanti-glare Corning® Gorilla® glass sheet with 10% transmission hazeunder compression. Data set 1205 represents a 1 mm thick creamy etchedanti-glare Corning® Gorilla® glass sheet with 40% transmission hazeunder tension. Data set 1207 represents a 1 mm thick creamy etchedanti-glare Corning® Gorilla® glass sheet with 40% transmission hazeunder compression. Data set 1209 represents a 1 mm thick Corning®Gorilla® glass sheet without anti-glare treatment as a control. As shownin FIG. 12, the creamy etched anti-glare glass sheets have comparableimpact resistance as compared to the control, i.e., standard Corning®Gorilla® glass without anti-glare treatment, both under tension andcompression. It is therefore believed that etched anti-glare glasssheets can be used in the laminated structures disclosed herein withouta substantial adverse effect on the structure's resistance to impact.

FIG. 13 is a Weibull plot demonstrating impact resistance for sol geltreated anti-glare glass sheets with 10% haze under tension orcompression as compared to Corning® Gorilla® glass without anti-glaretreatment. Data set 1301 represents a 1 mm thick sol gel treatedanti-glare Corning® Gorilla® glass sheet with 10% transmission hazeunder tension. Data set 1303 represents a 1 mm thick sol gel treatedanti-glare Corning® Gorilla® glass sheet with 10% transmission hazeunder compression. Data set 1305 represents a 1 mm thick Corning®Gorilla® glass sheet without anti-glare treatment as a control. As shownin FIG. 13, the sol gel anti-glare glass sheets under tension have alower impact resistance as compared to the control, i.e., standardCorning® Gorilla® glass without anti-glare treatment. However, the solgel treated anti-glare glass sheets under compression exhibit comparableimpact resistance as compared to the control. In a large majority ofapplications it is believed that the laminated structure will be undercompression (rather than tension) when the structures are loaded. It istherefore believed that sol gel treated anti-glare glass sheets can beused in the laminated structures disclosed herein without a substantialadverse effect on the structure's resistance to impact.

What is claimed is:
 1. A laminated structure comprising: a metal sheetincluding a first face and a second face with a thickness of from about0.1 mm to about 5 mm extending between the first face and the secondface; a first chemically strengthened or non-chemically strengthenedglass sheet having a thickness ranging from about 0.3 mm to about 2 mm;and a first interlayer attaching the first glass sheet to the first faceof the metal sheet.
 2. The laminated structure of claim 1, wherein thefirst interlayer comprises a layer of polyvinyl butyral or an ionomer.3. The laminated structure of claim 2, wherein the layer of polyvinylbutyral has a thickness ranging from about 0.1 mm to about 0.8 mm. 4.The laminated structure of claim 2, wherein the layer of ionomer has athickness ranging from about 0.1 mm to about 2 mm.
 5. The laminatedstructure of claim 1, wherein the first glass sheet comprises a glass orglass ceramic containing silver, copper or a combination of silver andcopper or comprises a glass or glass ceramic having a coating thereon,said coating containing silver, copper or a combination of silver andcopper.
 6. The laminated structure of claim 1, wherein the Young'smodulus of the first interlayer is greater than or equal to 15 MPa. 7.The laminated structure of claim 6, wherein the Young's modulus of thefirst interlayer is greater than or equal to 275 MPa.
 8. The laminatedstructure of claim 1, wherein the first glass sheet comprises anacid-etched glass sheet.
 9. The laminated structure of claim 1, whereinthe first glass sheet has a thickness ranging from about 0.5 mm to about1.1 mm.
 10. The laminated structure of claim 1, wherein the first glasssheet is chemically strengthened and comprises a glass selected from thegroup consisting of aluminosilicate glass and alkali-aluminoborosilicateglass.
 11. The laminated structure of claim 1, wherein the first glasssheet comprises at least one anti-glare surface and/or at least oneanti-microbial surface.
 12. The laminated structure of claim 1, furthercomprising: a second glass sheet including a thickness of less than orequal to about 2 mm; and a second interlayer attaching the second glasssheet to the second face of the metal sheet, wherein the second glasssheet is chemically strengthened.
 13. A method of manufacturing alaminated structure comprising: (i) providing a metal sheet including afirst face and a second face with a thickness ranging from about 0.1 mmto about 5 mm extending between the first face and the second face; (ii)providing a chemically strengthened or non-chemically strengthened glasssheet having a thickness of less than or equal to about 2 mm and atleast one anti-glare surface; (iii) attaching the glass sheet to thefirst face of the metal sheet with a first interlayer.
 14. The method ofclaim 13, wherein the glass sheet has a thickness ranging from about 0.3mm to about 1 mm.
 15. The method of claim 13, wherein the glass sheet ischemically strengthened and is selected from the group consisting ofaluminosilicate glass and alkali-aluminoborosilicate glass.
 16. Themethod of claim 13, further comprising the step of treating the glasssheet to produce the at least one anti-glare surface, wherein thetreating step is chosen from acid etching, creamy etching, masked acidetching, sol gel processing, mechanical roughening, and combinationsthereof.
 17. The method of claim 13, further comprising a step offurther strengthening the glass sheet, wherein the further strengtheningstep is chosen from acid etching.
 18. A method of manufacturing alaminated structure comprising: (i) providing a metal sheet including afirst face and a second face with a thickness of from about 0.1 mm toabout 5 mm extending between the first face and the second face; (ii)providing a glass sheet having a thickness of less than or equal toabout 2 mm; (iii) treating the glass sheet to produce at least oneanti-glare surface; (iv) optionally chemically strengthening the glasssheet; (v) optionally acid etching the glass sheet; and (vi) attachingthe glass sheet to the first face of the metal sheet with a firstinterlayer.
 19. The method of claim 18, wherein the treating step (iii)is chosen from acid etching, creamy etching, masked acid etching, solgel processing, mechanical roughening, and combinations thereof.
 20. Themethod of claim 18, wherein the chemical strengthening step (iv) ischosen from ion exchange processes.